Combination hydrocarbon vaporization and cracking process



Oct. `16, 1951 Filed Feb. 18. 1947 J. A. CROWLEY, J COMBINATION HYDROCARBON VAPORIZATION AND CRACKING PROCESS 2 Sheets-SheetI .l

Oct. 16, 1951 J. A. CROWLEY, JR 2,571,342

i COMBINATION HYDROCARBON VAPORIZATION AND CRACKING PROCESS Patented Oct. 16, 19/51 COMBINATION HYDROCARBON VAPORIZA- TION AND CRACKING PROCESS John A. Crowley, Jr., New York, N. Y., assignor to Socony-Vacuum Gil Company, Incorporated, a corporation of New York Application February 18, 1947, Serial No. 729,249

14 claims.

This invention pertains to a method for conversion of high boiling hydrocarbons to lower boiling hydrocarbon products containing substantial amounts of material boiling within the range of aviation and motor gasoline. The invention is particularly directed to an improved process for the continuous catalytic conversion to gasoline containing products of liquid hydrocarbon fractions which boil for the most part above the desired conversion temperature.

It is well known that high boiling hydrocarbons such as gas-oil, for example, when contacted in the vapor phase with a suitable solid adsorbent material at temperatures of the order of 800 F. and usually at pressures above atmospheric, may be converted to lower boiling gaseous, gasoline containing products. Until recently, most commercial catalytic hydrocarbon cracking processes have involved the use of selected cracking stock which consist of material which may be vaporized without undergoing substantial pyrolytic conversion prior to being contacted with the solid catalyst. Recently certain catalytic processes for handling heavier liquid charging stocks have been developed in which the heavy liquid petroleum charged is mixed with a hot catalyst coming from a catalyst regenerator so as to eiect vaporization of the liquid oil after which the mixed catalyst and oil vapors are passed through a conversion Zone to'veiect linal conversion of the vaporized hydrocarbons to gasoline containing products. In lsuch processes the heat for vaporization of the liquid hydrocarbons and the heat of conversion thereof is all supplied by the hot regenerated catalyst initially contacted with the liquid oil. This means that the hydrocarbon charge is initially contacted with a very active catalyst at temperatures far in excess of the desired cracking conversion temperature at a relatively high catalyst to oil ratio, resulting in excessive dry gas and coke yields and inferior gasoline yields` Moreover, the total range of catalyst temperatures from the beginning to the end of its contact with the hydrocarbons is undesirably wide.

It has been the practice in thermal cracking operations to subject the very high boiling charging stocks to a preliminary thermal viscositybreaking step to lower the boiling range of the hydrocarbons and to prepare a suitable charging stock for thermal cracking operations. It has also been the custom to subject such high boiling charging stocks to a thermal coking operation whereby the high boiling liquid residuum is decomposed to yield a substantial amount of coke and non-ccndensible gas as well as a vaporized hydrocarbon fraction suitable for thermal cracking operations. It has recently been suggested that such a coking operation may be accomplished by bringing the liquid petroleum residuum into contact with a mass of inert refractory particles which have previously been heated so as to contain suicient sensible heat to supportthe coking reaction. Such a process has the disadvantage that the solid material must be preheated to a temperature far above the desired partial convertion temperature for the liquid petroleum charge in order that it may supply as sensible heat the amount of heat required for the reaction. As a consequence, the liquid petroleum charge is converted to excessive yields of coke and dry gas due to the undesirably high temperature of initial Contact with the freshly charged preheated solid inert material.

A major object of this invention is the provision of an improved continuous method of apparatus for preparing a vaporized petroleum charge for a continuous catalytic conversion process from a liquid petroleum charge which method substantially avoids the above described diiiiculties.

Another object of this invention is the provision in a continuous cyclic hydrocarbon conversion process of a continuous process for thermally viscosity-breaking a high boiling liquid hydrocarbon charge in the presence of a moving heated solid material to provide a vaporized hydrocarbon fraction suitable for use as a charge to said conversion process which viscosity-breaking process may be conducted at a narrow range of temperatures most suitable for conducting the viscosity-breaking reaction without excessive coke or dry gas formation.

A specic object of this invention is the provision of a combined moving bed catalytic cracking and moving bed hydrocarbon thermal viscosity-breaking process.

Another object is the provision of a practical continuous catalytic process capable of handling liquidV hydrocarbons boiling above the desirable average conversion temperature without substantial pyrolytic conversion thereof to coke and noncondensible gas.

Another specific object is the provision of an improved integral petroleum residuum viscositybreaking and catalytic cracking apparatus.

Another specific object is the provision in a continuous cyclic catalytic vapor hydrocarbon conversion process of an improved method and apparatus for vaporizing the hydrocarbon charge.

These and other objects of this invention will become more apparent from the following discussion of the invention.

The present invention in a broad form is one wherein a suitable liquid hydrocarbon charge is brought into contact with a substantially compact column of downwardly moving hot heat absorptive material in a confined partial conversion or vaporizing zone in which it is transformed either by conversion to lower boilingr hydrocarbons or insome instances'merely vaporized to provide a vaporized hydrocarbon fraction suitable for a catalytic conversion operation. Heat absorptive material consists of capsules containing a substance capable of giving up heat (usually by solidiiication) over a narrow range of temperatures which are suitable for effecting the desired partial conversion or vaporization of the liquid hydrocarbon charge. Used heat absorptive material is withdrawn from the partial conversion or vaporizing zone and heated heat absorptive material is supplied thereto at a rate sufficient to supply the heat required for the transformation ofthe liquid hydrocarbon "charge to said vaporized fraction. The used heat absorptive material is lthen heated in a separate heating zone usually by direct contact with a suitable heating gas which may, for example, be a `Ilue gas or a heat exchange gas containing sensible heat from the regeneration zone of the catalytic conversion process. The heated heat absorptive material having absorbed a substantial amount of latent heat is then returned to the partial conversion or vaporizing zone as the supply thereto. The resulting vaporized hydrocarbon fraction is passed to a catalytic conversion zone wherein it is contacted with a suitable nnely divided adsorbent catalyst wherein to effect the desired conversion, for example, a cracking conversion to gaseous, gasoline containing products. The used catalyst is passed through a suitable regeneration zone wherein the Vcontaminant deposit thereon is removed by burning and is then returned to the conversion zone. The actual catalytic conversion reaction involved in the conversion zone may be a vapor phase hydrocarbon cracking reaction or any of a number of other reactions, for example, catalytic hydrogenaton, dehydrogenation, polymerization, isoforming, alkylation, reforming, aromatization, partial oxidation, desulfurizing, etc., of the vaporized hydrocarbon charge.

'While it is contemplated that the heat adlsorbent material should move through the vaporizng or partial conversion zone as a substantially compact column according to the method of this invention, it is contemplated that within the scope of this invention the catalyst in the cyclic catalytic conversion system may move either Vas a powdered catalyst suspension in the hydrocarbon vapors or as a fluidized mass or as a granular catalyst moving as a substantially compact bed. In its preferred form this invention contemplates the use of a moving bed type catalytic conversion process because of certain important operational advantages which will become apparent in the following discussion.

The contact material employed may partake of the nature of natural or treated clays, bauxites, or synthetic associations of silica, alumina or silica and alumina. Also the catalyst may take the form of mixtures of metallic oxides, particularly of those from the III and VI groups of the periodic system to which mixture oxides of silica may be added. Other catalysts may consist of carriers such as alumina, Carborundum, etc., upon which promoters, usually consisting of certain metallic oxides have been deposited. The exact nature of the catalyst employed will vary depending upon the particular hydrocarbon reactants involved and upon the type of conversion to be accomplished. The size of the catalyst particles will vary depending upon the type process involved. For suspension type processes the catalyst will be in the form of a powder of about 100 mesh and nner as determined by Tyler standard screen analysis. For the moving bed type process the contact material may consist of particles ranging from below 4 mesh to about 60 mesh and preferably from about 4 to 16 mesh.

The size and shape of the capsules of heat absorbent material used in this invention, it will be understood of course, are matters capable of considerable variation Without departing from the spirit of this invention. In general it has been found that capsules having an average diameter within the range of about 2 to 8 mm. are satisfactory, but itis not intended that this invention be limited to capsules within that size range or to capsules that are spherical in shape. The heat absorbing substance within the capsules should be one capable of releasing a substantial amount lof heat over a narrow range of temperatures which are at a level suitable for the partial conversion or vaporization of the liquid hydrocarbon charge without excessive conversion thereof to gas and coke and above the condensation temperature of the resulting vaporized hydrocarbon fraction. It will be apparent that the material within the capsules should be chosen with reference to the particular liquid hydrocarbon charged and the most suitable temperature for its transformation to the desired vaporized hydrocarbon fraction. Typical substances for use in such capsules and a typical capsule which may be employed in the process of this invention aredescribed in my United States Patent 2,244,612 issued June 3, 1941. Preferably the material employed within lthe capsules should be a fusible material such as a metal, alloy or inorganic salt or mixtures thereof, having a melting point broadly within the range about '750 F. to 1100 F. and preferof such substances are the following:

Fusible Substance F.

Lithium Bromide Lead Chloride Cupric Bromide P-b+20% Na. 788 Zn 788 Zu+l0% Al 797 70% Zn+30% A1 950 80% 13H-20% Sb 761 70% 13H-30% Sb 878 60% 13H-40% Sb 968 90% zml-10% Sb 878 40% Pb+60% Sb 914 70% Mg+30% A1 811 33% Mg+67% Al.. 838 34% Mg|66% Pb. 858 72% Mg-|-28% Ni D50 23.8% Gu+65.2% Al 1009 61% Mg+39% S11 1049 These materials absorb a substantial amount of 'latent heat of fushion upon being melted and liberate that heat upon solidifying. For example the heat of fusion by calculation of some of the materials listed above is as follows:

70% Mgg-30% Al, heat of fusion '76.6 ca1./gm.; '72% Mg+28% Ni, heat of fusion 72.3 cal./gm.; 23% C11-|-77% Sb, heat of fusion 39.6 cal/gm.

This invention may be most readily understood by reference to the drawings attached hereto of which Figure l is an elevational view of one preferred form of this invention, Figure 3 is a similar view, partially in section, of a modified form of the invention, and Figure 42 is an enlarged view of one of the capsules of heat absorptive matetained within capsules.

rial. All of these drawings are highly diagrammatic in form.

Turning now to Figure l, the system shown therein may best be understood with reference to conducting an exemplary process, for example, the conversion of a high boiling petroleum residuum consisting principally of material boiling above about 850 F. to lower boiling gasoline containing products may be considered. The high boiling liquid charge may be heated in a suitable conventional tubular heater I0 to a suitable temperature below which it undergoes substantial thermal cracking during the time interval in which it remains in heater I0. It then passes via conduit |I into the upper section of partial conversion vessel I2 wherein it is distributed into a substantially compact column of heat absorptive material entering vessel I2 from hopper I3 via feed leg Ill and leaving the lower end of vessel I2 through conduit I5. 'Ihe liquid hydrocarbon charge undergoes a pyrolytic viscosity-breaking reaction in vessel I2 so as to be converted into a lower boiling vaporized fraction, the heat for this reaction being supplied from the heat absorptive material as latent heat released by the -f solidication of a suitable fusible substance con- 'Ihe material within the capsule chosen may be, for example, 70% Zn+30% Al, having a melting point of about 950 F. for example, so that the entire viscosity-breaking reaction is conducted at a temperature level slightly below 950 F. A typical form of the heat absorptive bodies is shown in Figure 2, wherein we find the heat absorptive body |60 to be composed of a suitable metal shell IBI within which there is enclosed a suitable substance |62 as described capable of a substantial amount of heat at a substantially constant temperature level. Returning to Figure l, in many operations a certain( amount of carbonaceous material may be deposited upon the heat absorptive material, i. e. on the capsules during its passage through vessel I2. This deposit may be removed by directing the capsules via conduit I6 through a rotary drum I'I wherein they arel caused to be agitated and mixed with pebbles or steel balls or the like, introduced through conduit I6. The carbonaceous deposit is thus milled 01T of the capsules by abrasion and impact. The

mixture passes via conduit I9 to a suitable mevchanically agitated screen 26 wherein the capmaterial from the capsules may be substituted for that described, if desired. The carbonaceous material withdrawn at 23 may be recovered as a by-product from this process. The capsules pass via conduit 2| into the upper end of heater 25 and pass downwardly therethrough as a sub-V stantially compact column. A suitable heating gas which is substantially inert to the metal of which the capsules are made under the conditions involved is introduced into a suitable heater 26 which may be of the tubular type, heated to a temperature above that of the capsules, for

6 example, 1050 F., and then introduced through conduit 21 into heater 25. The heating gas passes upwardly through the column in heater 25 so as to supply latent heat for fusion of the substance within the capsules and is Withdrawn from heater 25 via conduit 28. The heating gas may be steam, flue gas, nitrogen and in some instances air, for example. Where the heating gas is air or flue gas, the heater 26 may consist of a simple conventional line burner. Alternatively instead of employing a heater 26, a suitable fuel gas may befintroduced to vessel 25 via conduit 30 and air may be introduced via conduit 3| to support combusion of the fuel gas in the column of heat absorptive material, thereby supplying the required heat, The heated heat absorptive material passes from heating zone 25 via conduit 32 to conveyor 33 by which it is transferred to duct 34 supplying the hopper I3. i

When the recovery as a by-product of the carbonaceous material deposited on the heat absorptive material is not desired, the used heat absorptive material from vessel I2 may be directed through conduits I5 and GII into the upper section of a separate vessel 6|. The heat absorptive material passes downwardly through vessel 6| while being contacted with air introduced at 62 which acts to burn off the carbonaceous material from the capsules. The resulting flue gas is withdrawn from vessel 6I via conduit 63. The heat released/by the burning of the carbonaceous material is absorbed as latent heat of fusion by the heat absorptive material. If more than the required amount of heat for complete fusion of the substance in the capsules is released by the burning reaction, the excess heat may be removed from vessel 6I by suitable means such as the recirculation of cold flue gas along with the air introduced at conduit 62. If the amount of carbonaceous deposit upon the capsules is not enough to release on burning suflicient heat for the hydrocarbon transformation in vessel I2, additional heat may be added by preheating of the air or air and flue gas introduced through conduit 62 to vessel 6 I The heated heat absorptive material passes from the lower end of vessel 6I via conduit 64 to conveyor 33 by which it is returned to hopper I3 supplying partial convertor IZ.

It will be apparent that by the method of this invention the heat absorptive material may enter the partial conversion zone I2 and discharge from that zone at substantially the same temperature, which is of the order of 950 F. in this example. Substantially the total heat for the transformation of liquid hydrocarbon charge to the vaporized fraction is supplied by the release of latent heat by the fusible substance within the capsules. In this manner, excessive conversion temperatures within the vessel I2 are entirely avoided. In order to prevent escape of gaseous hydrocarbons from either end of the vessel I2, an inert gaseous blanket may be maintained at either end of the vessel by introduction of a suitable gas such as steam or flue gas via conduits 35 and 36. The vaporized hydrocarbon fraction formed in vessel I2v is withdrawn from the lower section thereof through conduit 31 and introduced into the upper section of an elongated cracking conversion vessel 38. A suitable particle-form adsorbent catalyst from hopper 39 is introduced into the upper end of vessel 38 via gravity feed leg 40. The catalyst passes downwardly through vessel 38 as a substantially compact column, being withdrawn from the lower end of vessel 38 via conduit 4| at a suitable rate controlled by valve 42. The vaporized hydrocarbons pass downwardly through the catalyst column and are converted at a suitable temperature, for example, 850 F. to 950 F. to lower boiling gaseous, gasoline containing products which are withdrawn from the lower section of vessel 38 via conduit 43. It should be understood that the term gaseous as employed herein in Vdescribing and in claiming this invention is employed in a broad sense as meaning that the material involved exists in the gaseous phase under the particular conditions of temperature and pressure involved regardless of what may be the normal phase of that material under ordinary atmospheric conditions. An inert seal gas may be supplied into the upper end of vessel 38 through conduit 44 in order to maintain a seal gas blanket adjacent the upper end of vessel 38. An inert purge gas such as steam or flue gas may be introduced into the lower section of vessel 38 through conduit 45 to purge gaseous hydrocark bon products from the outflowing spent catalyst.

The spent catalyst may be transferred by means of conveyor 46 to duct 41 through which it passes into the upper end of regenerator 48. The catalyst moves downwardly through vessel 48 as a substantially compact column, being withdrawn in a regenerated condition from the bottom of vessel 48 via conduit 49. A combustion supporting gas such as oxygen or air is introduced into the vessel 48 via conduit 50 and contacts the catalyst therein so as to burn off of the catalyst the carbonaceous contaminant deposited thereon in the conversion vessel 38. Flue gas may be withdrawn from the upper section of vessel 48 via conduit Heat transfer tubes may be provided within the vessel 48 for the purpose of controlling the catalyst temperature below a heat damaging level. These tubes may be supplied with a suitable heat exchange iiuid through conduit 52 and the heat exchange fluid may be withdrawn from these heat transfer tubes through conduit 53. The regenerated catalyst may be transferred by conveyor 54 to duct 55 supplying the convertor supply hopper 39.

While the method of this invention is particularly adapted for the handling of high boiling liquid petroleum charges which substantially boil above the temperatures at which it is desirable to conduct the thermal viscosity-breaking and the catalytic cracking reactions, the invention is also applicable to processes involving lower boiling original liquid hydrocarbon charges, which may be vaporized at the desired conversion temperature without aserious thermal cracking thereof, for example, 'gasoils boiling up to about 800 F. and naphtha fractions. Ordinarily these fractions are vaporized in an external tubular heater before being charged to the catalytic conversion vessel. Such a procedure involves the consumption of a considerable amount of heating fuel from a source outside of the catalytic cracking system. An apparatus particularly well adapted for handling such vaporizable hydrocarbon charge fractions by the method of this invention is shown in Figure 3. In Figure 3 there is shown an elongated, vertical `vessel 18 closed on either end. Apartition 1| of downwardly tapered construction is provided across the vessel at an intermediate level along its length so as to divide .it into an upper vaporizing chamber 12 and a lower conversion chamber 13. Heat absorptive materi'alfrom hopper I3 is supplied to the upper Vend of vessel 10 via conduit I4, and passes into a seal chamber 16, defined by means of partition 11 in the upper end of vessel 10. An inert seal gas is introduced into chamber 16 via conduit 18. Heat absorptive material passes via tubes 19 depending from partition 11 into the vaporizing chamber 12. The heat absorptive material passes downwardly through chamber 12 as a substantially compact column and is withdrawn from the bottom of vaporizing chamber 12 via conduit which connects into the downwardly tapered partition 1|. A horizontal partition 8| extends across the lower section of the vaporizing chamber to define at its lower end a seal and purging chamber 82. The heat absorptive material passes through the partition 8| through uniformly distributed tubes 83 depending therefrom and is purged substantially free of gaseous hydrocarbons in chamber 82, before discharging through conduit 80, by a suitable inert purge gas such as steam introduced from manifold 85 to perforated pipes 88 which extend across chamber 82 and issuing from the pipes 86 into the mass of heat absorptive material in chamber 82. Hot particle form catalyst from hopper 39 is passed downwardly through gravity feed leg 40 into the seal chamber 88. The catalyst passes by gravity from a bed thereof in chamber 88 via conduit 90 into the upper section of chamber 13. An inert seal gas is introduced into chamber 88 via conduit 89 at a sufficient rate to maintain a seal gas pressure therein slightly higher than the gaseous pressure in the upper section of chamber 13. A stuffing box 9| is provided at the location of entry of conduit 901 into the side of vessel 10 to prevent escape of gas from chamber 13. The catalyst moves downwardly through chamber 13 as a substantially compact column being withdrawn at the lower end of Vessel 10 through conduit 92 at the desired rate controlled by valve 93. In order to insure uniform withdrawal of catalyst from all portions of the horizontal cross-sectional area of the conversion chamber 13 suitable baffling should be provided just above the control discharge conduit 92. In the modification shown the baiing takes the form of two vertically spaced horizontal partitions and 96 having orifices 91 and 98 therein. The orifices 91 in the upper partition 95 are uniformly distributed across the partition. The orifices 98 in partition 96 are less in number than the orifices 91 and are horizontally staggered with respect to orifices 91 so that each orifice 98 receives proportionate catalyst flow from a plurality of orifices 91. The streams from orifices 98 are then proportionately merged into the single outlet stream in conduit 92. An inert purge gas is introduced through conduit 99 to manifold |00 from which it passes through pipes |8| under a plurality of horizontally spaced gable-roofed inverted distributing troughs |02 positioned in the lower section of chamber 13. Thus the gaseous hydrocarbon products are substantially purged from the outflowing spent catalyst. A suitable liquid hydrocarbon charge, for example, a gas oil fraction boiling within the range about 450 F.-750 F. is introduced from manifold |05 into headers |06 which extend across the space |01 above the column of heat absorptive material in chamber 12. The liquid oil is then sprayed through nozzles |88 onto the column of heat absorptive material and is vaporized by the heat released in solidifying the substance within the capsules. For example, the substance within the capsules may be a fusible alloy consisting of 70% Bi and 30% Sb, melting at about 878 F. The oil charge is vaporized and heated to a temperature shortly below 878 F. by the time it reaches the lower section of chamber 12. The vaporized oil then passes into the conversion chamber 13 through tubes IIB, which are connected tightly through partition 1| and which slide upwardly through partition 8|. Inverted conical shaped baffles are supported by suitable means (not shown) above the tubes l I so as to provide disenga'ging surfaces for disengagement of the vaporized hydrocarbons from the column of heat absorptive material and so as to prevent the gravity iiow of heat absorptive capsules into the upper ends of tubes H0. The vaporized hydrocarbon charge passes downwardly through the column of catalyst in chamber 'I3 to become converted to gasoline containing products. These gaseous products are collected under one or more vertical rows of horizontally spaced inverted collecting troughs ||2 within the lower section of chamber 13. The gaseous products are withdrawn from troughs ||2 through pipes ||3 to manifold ||4 from which they are in turn withdrawn through outlet conduit ||5. The spent catalyst from chamber 13 is transferred via conveyor IIS to regenerator lll. The regenerator shown is of the multi-stage type, consisting of a plurality of burning stages IIS-|23 inclusive and a plurality of cooling stages |2||23 inclusive which alternate in vertical series with the burning stages. Air is supplied from manifold |24 to each of the burning stages through separate inlets |25|21 inclusive. Flue gas is withdrawn from the burning stages through separate outlets l28|30 inclusive to manifold |3|. If desired, heat transfer tubes or coils may be provided in the cooling stages l2 ||23 inclusive. Heat exchange uid may be supplied from manifold |32 to each of these cooling coils through inlet pipes |33 and withdrawn from these cooling coils through pipes |34 to an outlet manifold |35. In some'instances it is desirable to eliminate the heat transfer tubes and to pass a suitable substantially oxygen free cooling gas directly through the catalyst bed in each cooling stage to accomplish heat removal from the catalyst. In such instances the manifold |32 and pipes |33 may serve as inlets for said cooling gas and the pipes |34 and manifolds |35 may serve as withdrawal means for the heated gas. The regenerated catalyst is withdrawn from the bottom of the regenerator through conduit |38 at a suitable rate controlled by valve |39. The regenerated catalyst is transferred by conveyor |4| to duct |42 supplying the hopper 39. The used heat absorptive material passes by gravity via discharge conduit 80* to the reconditioner |43. It moves downwardly through the reconditioner |43 being withdrawn from the bottom thereof through conduit |44. Hot ilue gas from the burning sta-ges of the regenerator existing at a temperature of the order of 950 111-1150 F. is directed from manifold |3| through duct |45 into the lower section of reconditioner |43. The hot iiue gas passes upwardly through the column of heat absorptive material so as to supply heat for melting the fusible alloy in the capsules of heat absorptive material. If sufficient heat is not available from the regenerative iiue gas, additional heat may be obtained or all the required heat may be obtained by directing the hot heat exchange gas from cooling stages |2| to |23 inclusive from manifold into duct |45 and thence into reconditioner |43. The relative amount of gas Withdrawn from manifolds |3| and |35 may be regulated by means of valves |41 and |48 respectively thereon. The cooled gases may be withdrawn from the upper section of reconditioner |43 through conduit |43.V In the instant example, these e'iluen't gases may exist at a temperature of ,the order of 875 Iii-885 F. The heated heat absorptive material passes from vessel |43 through conduit |44 to conveyor |50 by which it is returned to hopper I3.

The arrangement shown in Figure 3 may be employed also for the conversion of liquid petroleum residua in which event the chamber 12 serves as a partial conversion or Viscosity-breaking Zone. Any carbonaceous material deposited upon the capsules may be burned off by means of air introduced to reconditioner |43 at |5|. In some instances where the amount of heat recoverable from the regeneration Zone is insuiiicient for vaporizing or partially converting the liquid petroleum charge, additional heat may be supplied to the systemby introduction of a suitable fuel gas into the vessel |43 through conduit |52 to be burned in contact with the heat absorptive material by air introduced into vessel |43 at |5|.

It will be understood that this invention is not intended to be limited to the particular details of apparatus design and arrangement hereinabove described. For example, other types of catalyst regenerators adapted to accomplish removal of the carbonaceous contaminant by burning at controlled temperatures may be substituted for the preferred forms which are shown. lAlso methods for introducing and withdrawing solid material into and from the various vessels other than those shown may be employed. Moreover other constructions for distributing gases into the several vessels and for removing gases therefrom may be employed. It is also not intended that the invention be limited to the particular details of operating conditions and process applications specifically described hereinabove or otherwise limited except as limited in the following claims.

I claim: Y

1 In a continuous cyclic hydrocarbon conversion process wherein a finely divided adsorbent contact material is passed cyclically through a hydrocarbon conversion zone vwherein it contacts a Vaporized hydrocarbon charge to effect the conversion thereof to lower boiling gasoline containing products and through a contact material regeneration zone wherein carbonaceous contaminants deposited upon the contact material during said hydrocarbon conversion are burned, the method for conditioning a high boiling liquid fraction to provide therefrom a K suitable vaporized hydrocarbon charge for said conversion zone which comprises: maintaining a substantially compact column of downwardly moving heat absorptive material in a confined partial conversion zone, passing said high boiling liquid fraction into contact with said column to effect its conversion to a lower boiling vaporized hydrocarbon fraction suitable for charging to said conversion zone, said conversion resulting in the deposition of a carbonaceous deposit upon said heat absorptive material, passing said vaporized fraction to said conversion Zone as the hydrocarbon charge thereto, substantially continuously withdrawing used heat absorptive material bearing carbonaceous deposit from the lower section of said partial conversion zone and supplying heated heat absorptive material into the upper section of said partial conversion zone at a rate controlled to supply the heat required for the conversion of said liquid fraction to said vaporized fraction, physically effecting the realsdan" 11 moval of carbonaceous deposit from said used heat absorptive material, separating the contact material from the removed carbonaceous material and passing it through a separate heating zone, passing a suitable heating gas into contact with said heat absorbing material in said heating zone to cause said material to absorb a substantial amount of heat, returning the heated heat absorptive material to said partial conversion zone as the supply thereto, said heat absorptive material being capsules containing a fusible substance capable of releasing latent heat at a temperature level below that at which excessive conversion of said liquid hydrocarbon fraction to gas and coke would occur and above that at which said vaporized hydrocarbon fraction formed in said partial conversion zone will condense.

2. The method for conversion of high boiling liquid hydrocarbons to lower boiling gaseous gasoline containing products which comprises: maintaining a substantially compact column of downwardly moving heat absorptive material in a confined partial conversion Zone, said heat absorptive material being capsules containing a fusible substance capable of fusing with the absorption of substantial latent heat and solidifying with therelease of substantial latent heat at a relatively narrow temperature level within the range about 750 F. to 1100 F., passing said high boiling liquid fraction into contact with said column to eiect its conversion at a temperature level within the range about 750 F. to 110 0 F. to a lower boiling vaporized hydrocarbon fraction, said conversion resulting in the deposition of a carbonaceous deposit upon said heat absorptive material, substantially continuously withdrawing used heat absorptive material bearing carbonaceous deposit from the lower section of said partial conversion zone and supplying heated heat absorptive material into the upper section of said partial conversion zone at a rate controlled to supply the heat required for the conversion of said liquid fraction to said vaporized fraction, effecting removal of carbonaceous deposit from said heat absorptive material by mechanical attrition and separating the removed carbonaceous material from the heating absorbing material, passing the separated heat absorptive material through a confined heating zone, passing a suitable heating gasV in contact With said heat absorptive material in said heating zone to effect a substantial absorption of latent heat of fusion by said heat absorptive material, returning the heated heat absorptive material to said partial conversion zone as the supply thereto, passing said vaporized fraction from said partial conversion zone into contact with said catalyst in said conversion zone to effect the conversion of said vaporized fraction to lower boiling gaseous, gasoline containing products, withdrawing said gaseous products from said conversion zone, withdrawing the spent catalyst from said conversion zone substantially separately of said gaseous products, passing said spent catalyst through a conned regeneration zone while controlling its temperature below a heat damaging level, contacting said catalyst in said regeneration zone with a combustion supporting gas to burn the carbonaceous contaminant on said catalyst, and returning regenerated catalyst from said regeneration zone to said conversion zone.

3. The method for conversion of high boiling liquid petroleum residuums to lower boiling gaso- 12 line containing products in the presence of` a particle-form catalyst which method comprises: maintaining a substantially compact column of downwardly gravitating heat absorptive material in a confined viscosity breaking zone, said heat absorptive material consisting of capsules containing a substance having a fusion temperature level below that temperature level within the range about 800 F. to 1000 F., passing said liquid residuum into contact with said column to effect a viscosity-breaking thereof resulting in its conversion to a vaporized hydrocarbon fraction and resulting in the deposition of a carbonaceous deposit on said capsules, substantially continuously withdrawing used capsules bearing carbonaceous deposit from said viscosity-breaking zone, mechanically effecting the substantial removal of carbonaceous deposit from said capsules, passing the capsules as a substantially compact column through a conned heating Zone, passing a suitable gaseous fuel and an oxygen containing gas into contact with said capsules in said heating zone in such quantities as to burn said fuel and effect a substantial increase in the latent heat content of said heat absorptive material, returning the heated heat absorptive material to said viscosity breaking zone at a sufhcient rate to supply the heat required or the viscosity-breaking conversion of said liquid residuum thereon to said vaporized fraction, passing a particle-form adsorbent catalyst as a substantially compact column through a confined conversion zone at a temperature suitable for supporting the conversion of said vaporized fraction from said partial conversion zone, passing said vaporized fraction from said viscosity-breaking zone into contact with said catalyst in said conversion zone to effect the conversion of said vaporized fraction to lower boiling gaseous, gasoline containing products, withdrawing said gaseous products from said conversion zone, withdrawing the spent catalyst from said conversion zone substantially separately of said gaseous products, passing said spent catalyst through a conned regeneration zone while controlling its temperature below a heat damaging level, contacting said catalyst in said regeneration Zone with a combustion supporting gas to burn the carbonaceous contaminant on said catalyst, and returning regenerated catalyst from said regeneration zone to said conversion zone.

4. In a hydrocarbon conversion process wherein a vaporized hydrocarbon charge is contacted in a conversion zone with a finely divided contact material to effect conversion thereof to lower boiling products the method for conditioning a high boiling liquid hydrocarbon fraction to provide therefrom a suitable vaporized hydrocarbon charge for said conversion zone which comprises: maintaining a substantially compact column of downwardly moving heat absorptive material in a confined partial conversion zone, passing said high boiling liquid fraction into contact with said column to effect its conversion to a lower boiling vaporized hydrocarbon fraction suitable for charging to said conversion zone, said conversion resulting in the deposition of a carbonaceous deposit upon said heat absorptive material, passing said vaporized fraction to said conversion zone as the hydrocarbon charge thereto, supplying heated heat absorptive material into one end of said partial conversion zone at a rate controlled to supply the heat required for the conversion of said liquid fraction to said vaporized fraction, withdrawing used heat absorptive material bearing carbonaceous deposit from the lower section of said partial conversion zone, physically effecting the-removal of carbonaceous deposit from said heat absorptive material, separating the heat absorptive material from the removed carbonaceous material and heating it in a separate heating zone to cause said material to absorb a substantial amount of heat, returning the heated heat absorptive material to said partial conversion Zone as the supply thereto, said heat absorptive material being capsules containing a fusible substance capable of releasing latent heat at a temperature level below that at which excessive conversion of said liquid hydrocarbon fraction to gas and coke would occur and above that at which said vaporized hydrocarbon fraction formed in said partial conversion zone will condense.

5. The method for conversion of high boiling liquid hydrocarbons to lower boiling gaseous gasoline containing products which comprises: maintaining a substantially compact column of downwardly moving heat absorptive material in a confined partial conversion zone, passing said high boiling liquid fraction into contact with said column in the upper section of said partial conversion zone and moving it downwardlyV within said zone to eifectits conversion to a lower boiling vaporized hydrocarbon fraction, substantially continuously withdrawing used heat absorptive `material in the absence of adsorptive catalytic material from the lower section of said partial conversion zone at a temperature suitable for said hydrocarbon conversion and supplying only heated heat absorptive material in the absence of adsorptive catalytic material into the upper section of said partial conversion zone at a temperature substantially the same as that at which said absorptive material is withdrawn from said zone and at a rate controlled to supply the heat required for the conversion of said liquid fraction to said vaporized fraction, passing the used heat absorptive material withdrawn from said partial conversion zone in the absence of intervening admixture with any other solid contact material to and through a separate heating zone while contacting it therein with a suitable gas to effect a substantial addition of heat to said heat absorptive material, passing heated heat absorptive material to said partial conversion zone as the supply thereto, said heat absorptive material being capsules containing a fusible substance capable of releasing latent heat at a temperature level below that at which excessive conversion of said liquid hydrocarbon fraction to gas and coke would occur and above that at which said vaporized hydrocarbon fraction formed in said partial conversion zone will condense, maintaining a substantially compact column of downwardly moving adsorbent particle-form catalyst within a conned conversion zone, withdrawing said partially converted vaporized fraction from the lower section of said partial conversion zone and passing it into contact with said catalyst in said conversion zone to eect its conversion at a suitable temperature level to lower boiling gasoline containing products in the absence of heat absorptive material from said partial conversion and heating zones, withdrawing used catalyst bearing carbonaceous contaminant deposits from the lower section of said conversion zone, passing said used catalyst directly to a confined regeneration zone separate from said heating zone and passing it as a substanuauy compact column through said' regenera-v tion zone in the absence of said heat absorptive material while contacting it with an oxygen containing gas to substantially burn 01T said carbonaceous deposit, removing heat from said catalyst undergoing regeneration to control its tempera-4 ture below a level which would cause permanent damage in its eiectiveness for said hydrocarbon conversion, withdrawing regenerated catalyst from said regeneration zone and introducing said catalyst directly into the upper section of said conversion zone at a temperature suitable for said hydrocarbon conversion while excluding said catalyst from either of said partial conversion and heating zones.

6. In a continuous cyclic hydrocarbon conversion process wherein a finely divided adsorbent contact material is passed cyclically through a hydrocarbon conversion zone wherein it contacts a vaporized hydrocarbon charge to eifect the conversion thereof to lower boiling gasoline containing products and through a contact material rev generation zone wherein carbonaceous contaminants deposited upon the contact material during said hydrocarbon conversion are burned, the method for conditioning a high boiling liquid fraction to provide therefrom a suitable vaporized hydrocarbon charge for said conversion zone which comprises: maintaining a substantially compact column of downwardly moving heat absorptive material in a confined partial conversion zone, which is maintained out of solid material flow communication with said conversion and regeneration zones, introducing said high boiling liquid fraction into said column at a level spaced a substantial distance above its lower end, causing the liquid fraction to move downwardly within said column to effect its conversion to a lower boiling vaporized hydrocarbon fraction suitable for charging to said conversion zone, the entire conversion of said liquid fraction to vaporized hydrocarbons being conducted in the absence of said adsorbent contact material, withdrawing said vaporized fraction separately of the heat absorptive material from said partial conversion zone and introducing it to said conversion zone as a vapor phase hydrocarbon charge thereto while entirely excluding said heat absorptive material from said conversion zone, supplying heated heat absorptive material in the absence of said adsorbent contact material to the upper section of said partial conversion zone at a rate and temperature controlled to effect supply by said heat absorptive material of the heat required for said conversion of said liquid fraction to said lower boiling vaporized fraction, withdrawing said heat absorptive material from the lower section of said partial conversion zone at a temperature not substantially below that of its supply to the upper section of said Zone, heating; the withdrawn heat absorptive material in a con-- fined heating zone which is separate from said'. regeneration zone and returning the heated heat, absorptive material to said partial conversion. zone as the supply thereto, said heat absorptive material being capsules containing a fusible substance capable of releasing latent heat at a tem-A perature level below that at which excessive conversion of said liquid hydrocarbon fraction to= gas and coke would occur and above that at which. said vaporized hydrocarbon fraction formed insaid partial conversion zone will condense.

7. The method for conversion of high boiling liquid hydrocarbons to lower boiling gaseous. gasoline containing products which comprises:

15r maintaining a substantially compact column or downwardly moving heat absorptive material in a confined partial conversion zone, passing said high boiling liquid fraction into contact with said column in the upper section of said partial conversion zone and passing it downwardly within said column concurrently with the moving absorptive material to effect its conversion to a lower boiling vaporized hydrocarbon fraction, withdrawing said vaporized fraction from said column, separately of the heat absorptive material, replenishing said column solely by supplying heated heat absorptive material into the upper section of said partial conversion zone at a rate controlled to supply the heat required for the conversion of said liquid fraction to said vaporized fraction, withdrawing only used heat absorptive material from the lower section of said partial conversion zone at substantially the same temperature as that of the heat absorptive material supply to said zone, and passing it to a conned heating zone without intervening admixture with any other solid contact material, heating said heat absorptive material alone in said heating zone to add latent heat thereto and returning the heated heat absorptive material to said partial conversion zone as the supply thereto, said heat absorptive material consisting solely of capsules containing a fusible substance capable of releasing latent heat at a temperature level below that at which excessive conversion of said liquid hydrocarbon fraction to gas and coke would occur and above that at which said vaporized hydrocarbon fraction formed in said partial conversion zone will condense, passing a particle form adsorbent catalyst as a substantially compact column through a conned conversion zone entirely in the absence of said heat absorptive material at a temperature suitable for supporting a catalytic hydrocarbon conversion, passing said vaporized fraction withdrawn from said partial conversion zone into contact with the catalyst in said conversion zone in absence of said heat absorptive material to effect the conversion of said vaporized fraction to lower boiling gaseous, gasoline containing products, withdrawing said gaseous products from said conversion zone, withdrawing the spent catalyst from said conversion zone substantially separately of said gaseous products, passing said spent catalyst through a conned regeneration zone separate from said heating zone while controlling its temperature below a heat damaging level, contacting said catalyst in said regeneration zone with a combustion supporting gas to burn the carbonaceous contaminant on said catalyst, returning regenerated catalyst from said regeneration zone to said conversion zone.

8. The method for conversion of high boiling liquid hydrocarbons to lower boiling gaseous gasoline containing products which comprises: maintaining a substantially compact column of downwardly moving heat absorptive material in a confined partial conversion zone, passing said high boiling liquid fraction into contact with said col- -z umn in an upper portion of said partial conversion zone and passing it downwardly concurrently with the heat absorptive material ow to effect its con'- version to a lower boiling vaporized hydrocarbon fraction, withdrawing only used heat absorptive material from the lower section of said partial conversion zone and passing it to a conned heating zone without intervening admixture with any other solid contact mass material, said heat absorptive material consisting of capsules containing a fusible substance capable of releasing latent heat at a temperature level below that at which excessive conversion of said liquid hydrocarbonv fraction to gas and coke would occur and above that at which said vaporized hydrocarbon fraction formed in said partial conversion zone will condense, heating said heat absorptive material in said heating zone to add latent heat thereto and passing the heated material into the upper section of said partial conversion zone as the only solid material supply thereto, controlling the rate of heat absorptive material supply to said partial conversion zone sufficiently high to supply the heat required for the conversion of said liquid fraction to said vaporized fraction without the heat absorptive material undergoing any substantial change in temperature in passing through said partial conversion zone, withdrawing said vaporized fraction from the lower section of said partial conversion zone separately of said heat absorptive material and passing it in the absence of said heat absorptive material into contact with a substantially compact column of adsorbent catalyst moving through a separate conned conversion zone to effect conversion of said vaporized fraction to lower boiling gasiform, gasoline containing products, said conversion and partial conversion zone being maintained isolated from each other as regards solid material flow, passing spent catalyst from said conversion zone through a confined regeneration zone maintained separate from said heating zone, contacting said catalyst in said regeneration zone with a combustion supporting gas to burn the carbonaceous contaminant on said catalyst, withdrawing regenerated catalyst from said regeneration zone and returning it to said conversion zone at a temperature, suitable for supporting the hydrocarbon conversion therein, effecting the removal in a hot gaseous stream of a substantial portion of the heat released by contaminant combustion from said regeneration zone, and passing said hot gaseous stream into contact with the heat absorptive material in said heating zone to supply at least a portion of the required latent heat thereto.

9. The method for conversion of high boiling liquid hydrocarbons to lower boiling gaseous gasoline containing products which comprises: maintaining a substantially compact column of downwardly moving heat absorptive material in a confined partial conversion zone, passing said high boiling liquid fraction into contact with said column in an upper portion of said partial conversion zone and passing it downwardly concurrently with the heat absorptive material flow to effect its conversion to a lower boiling vaporized hydrocarbon fraction, withdrawing only u'sed heat absorptive material from the lower section of said partial conversion zone and passing itto a confined heating zone without intervening admixture with any other solid contact mass material, said heat absorptive material consisting of capsules containing a fusible substance capable of releasing latent heat at a temperature level be'- low that at which excessive conversion of said liquid hydrocarbon fraction to gas and coke would occur and above that at which said vaporized hydrocarbon fraction formed in said partial conversion zone will condense, contacting said heat absorptive material in said heating zone with a'. heated gas to eiect a substantial addition of latent heat to said heat absorptive material, passing the heated material into the upper section o! said partial conversion zone as the only solid material supply thereto, controlling the rate of heat 17\ absorptive material supply to said partial conversion zone suiiiciently high to supply the heat required for the conversion of said liquid fraction to said vaporized fraction without the heat absorptive material undergoing any substantial change in temperature in pasing through said partial conversion zone, withdrawing said vaporized fraction from the lower section of said partial conversion zone separately of said heat absorptive material and passing it in the absence of said heat absorptive material into contact with a substantially compact column of adsorbent catalyst moving through a separate confined conversion zone to effect conversion of said vaporized fraction to lower boiling gasiform, gasoline containing products, said conversion and partial conversion zone being maintained isolated from each other as regards solid material flow, passing spent catalyst from said conversion zone through a conned regeneration zone maintained separate from said heating zone, contacting said catalyst with an oxygen containing gas to substantially burn oi said carbonaceous deposit, withdrawing regenerated catalyst from said regeneration zone and introducing it into the upper section of said conversion zone at a temperature suitable for said hydrocarbon conversion, passing a suitable heat exchange gas in heat exchange relationship with said column in said regeneration zone to remove at least the major portion of the heat released by burning said carbonaceous deposit as increased sensible heat in said heat exchange gas and passing the hot heat exchange gas from said regeneration zone to said heating zone as said suitable heating gas supplied thereto.

10. In a continuous cyclic hydrocarbon conversion process wherein a nely divided adsorbent contact material is passed cyclically through a hydrocarbon conversion zone wherein it contacts a vaporized hydrocarbon change to eii'ect the conversion thereof to lower boiling gasoline containing products and through a contact material regeneration zone wherein carbonaceous contaminants deposited upon the contact material during said hydrocarbon conversion are burned, the method for conditioning a high boiling liquid fraction to provide therefrom a suitable vaporized hydrocarbon charge for said conversion zone which comprises: maintaining a substantially compact column of downwardly moving heat absorptive material within a confined partial conversion zone, which is maintained out of solid material flow communication with said conversion zone, passing a high boiling liquid hydrocarbon charge into the upper section of said column and passing it downwardly within said column to effect its conversion to a lower boiling vaporized hydrocarbon fraction with an accompanying deposition of a carbonaceous deposit upon said heat absorptive material, the entire conversion of said liquid fraction to said Vaporized fraction being conducted in the absence of said adsorbent contact material, withdrawing said vaporized fraction separately of the heat absorptive material from said partial conversion zone and introducing it to said conversion zone as a vapor phase hydrocarbon charge thereto while entirely excluding said heat absorptive material from said conversion zone, withdrawing used heat absorptive material from the lower section of said partial conversion zone and Apassing it to a confined heating zone maintained separate from said regeneration zone, passing a combustion supporting gas into contact with said heat absorptive material in said heating zone to burn said carbonaceous deposit thereon and thereby cause said heat absorptive material to absorb latent heat, passing the heated heat absorptive material in the absence of said adsorbent contact material into the upper section of said partial conversion zone at a rate controlled to supply by said material the heat required for said conversion of said liquid fraction to said lower boiling vaporized fraction without any substantial change in the temperature of the heat absorptive material in passing through said partial conversion zone, said heat absorptive material consisting of capsules containing a fusible substance capable of releasing latent heat at a temperature level below that at which excesive conversion of said liquid hydrocarbon fraction to gas and coke would occur and above that at which said vaporized hydrocarbon fraction formed in said partial conversion zone will condense.

11. The method of claim 10 further characterized in that said fusible substance in said capsules is capable of fusing with absorption of latent heat and solidifying with the release of latent heat within a relatively narrow temperature range within the broader range about 800 F. to 1000 F'.

l2. The method for converting high boiling liquid hydrocarbons to lower boiling gasoline containing products comprising, passing a particle form catalyst cyclically through a conversion zone and through a regeneration zone in each of which it ows downwardly as a substantially compact column, passing a heat absorptive vmaterial cyclically through a vaporizing zone and a heating zone in each of Which it flows downwardly as a substantially compact column of gravitating pieces of solid material, said vaporizing and heating zones being entirely isolated from said conversion and regeneration zones a's regards solid material'low so that the catalyst and heat absorptive material streams are maintained at all times separate, said heat absorptive material consisting of capsules containing a fusible substance capable of undergoing fiwion with the absorption of latent heat and solidi'cation with the release of latent heat over a narrow range of fusion temperatures within the broader range about '750 F. to 1l00 F., introducing liquid hydrocarbon charge into the upper section of said vaporizing zone and passing it downwardly within said column to effect its transformation to a vaporized hydrocarbon fraction, withdrawing said vaporized fraction from the lower section of said vaporizing zone separately of said heat absorptive material, passing said vaporized fraction in the absence of said heat absorptive material to and through said conversion zone as the vaporized `charge thereto, maintaining the catalyst temperature in said conversion zone at a level which will eiTect conversion of said vaporized fraction to a gasoline containing product, substantially continuously withdrawing heat absorbent material fro-m one end of said vaporizing zone substantially at the desired hydrocarbon transformation temperature and supplying heated heat absorbent material in the absence of the adsorbent material from said conversion and regeneration zones into the opposite end of said vaporizing zone at substantially the same temperature as that of said heat absorptive material withdrawn from said vaporizing zone and at a rate controlled to supply the heat required to eect said hydrocarbon transformation, heating the heat absorptive material withdrawn from said zone in a separate heating zone which is separate from said regeneration zone and returning the heated hea-t absorptive material to said vaporizing zone zas the .supply thereto, said heat absorptive mate- Arial'being capsules containing a substance capable -of releasing a substantial amount of heat at a relatively narrow temperature range which is ,suitable for effecting said hydrocarbon transformation.

13.1n a continuous cyclic hydrocarbon conversion process wherein a nely divided adsorbent `catalyst; is passed cyclically through a hydrocarbonconversion zone wherein it contacts a vaporizedhydrocarbon charge to effect the conversion thereof and through aregeneration zone wherein carbonaceous contaminants deposited on said catalyst are burned off by the action of a corn- `'bustion'supporting gas, the method for preparing the vaporized hydrocarbon charge for said proc- `,ess which comprises: :passing a heat absorptive material as a substantially compact column ,throug'h'a conned partial conversion zone maintafined'out of the solid flow path of said conver- :sion zone, 'without substantial drop in its temperature, `said heat absorptive material consisting of capsules containing a substance capable of undergoing fusion with the absorption of latent heat and solidioation with release of latent 'heat .at a narrow range of fusion temperatures within the broader range 800 F. to 1000o F., introducing a, high boiling liquid .hydrocarbon charge into said column vin an 4upper portion of said Ypartial conversion ,zone and passing it downwardly within said :column concurrently with the heat absorptive :material to effect its conversion entirely in .the -absence of said adsorbent catalyst to a lower boiling gasiform fraction, withdrawing said gasi- Iorm :fraction from the lower section of said par- 'tial conversion zone separately of said heat 'ab- -sorptive material and passing it in the absence `of said heat absorptive material 'to .said Converrzone 3as the Icharge thereto, vsubstantially continuously lwithdrawing used heat absorptive material from the lower section 'of said partial conversion zone 'at a temperature level `within `said narrow range of fusion temperatures and ,suppl-ying heated heat absorptive material into :the 'upper section of said partial conversion zone at atemperature level within said narrow Arange of .fusion 'temperatures and at a rate controlled to supply the heat required for 1the conversion of -said liquid fraction to said 'gasiform fraction, passing the used heat absorptive material with- :o'ut intervening admixture `with 'said `catalyst from said partial conversion zone'to a conflnedheating -zone maintained "separate "of 'said regeneration zone, introducing a suitable fuel gas and a suit- `.able :combustion supporting gas `into 'said .heating zone to 'burn said fuel gas Ain contact with said :heat absorptive material Yso as to supply a subsstantial amount of heat to be absorbed as latent .heat fof #fusion by said heat absorptive material .and passing the heat absorptive material from said heating zone `to said partial conversion zone .as-only solid material supply thereto.

14. The method for conversion of liquid hyfdrocarbons which comprises: passing a capsule form heat `absorptive material through a closed cyclic path 'including a partial conversion zone andza. heating zone in each of which zones it flows downwardly as asubstantially compact column, vsaid heat absorptive material comprising capsules 'containing a substance capable of undergoing fusion with the adsorption of latent Vheat and lsolidifcation with .the release of latent heat over 'a narrow range rof fusion temperatures within :the Ybroader range about '150 F. to l100 F.,

-compact column while being contacted with Aa suitable oxygen containing gas to burn from the contact material carbonaceous material deposited thereon in said 'conversion zone, Ymaintaining the heat absorptive capsules flowing in vsaid rst named cyclic path at all times separated from the rcontact material flowing Ain said 'second named cyclic path, introducing a suitable high boiling liquid rhydrocarbon charge into the upper .section vof said column and passing it downwardly therein to effect cracking conversion 'of said 'liquid charge to a lower boiling, vaporized .hydrocarbon fraction, said conversion being ac- -complishedfentirely in the absence of said 'adsorbent contact material, withdrawing said vaporized fraction from 'the lower section of said partial A'conversion zone separately of `the heat absorptive 'material and passing it into 'said conversion zone entirely in the vabsence of said Yheat 'absorptive material as the vaporized charge to 'said conversionzona supplying heated heat absorptive material at a temperature level within said 'narrow range of fusion temperatures into the fupper end of said .partial conversion .zone at a rate Vcontrolled to supply the heat required "to eiectsa'idconversion of the liquid charge to Asaid vaporized fraction, 'withdrawing used heat absorptive lmaterial from the v'opposite end of :said 'zone 'still ata temperature level within said narrow Vrange o'f .fusion temperature passing said -used .heat vabsorptive material `to rsaid Vheating zone without .intervening vadrnixture with said adsorbent :contact material, heating the heat absorptive material in'said `heating zone to supply fusion heatto said'substance'within said capsules and returning the 'heated heat absorptive material `tosaid partial conversion zone as the supply thereto.

JOHN A. CROWLEY, JR.

REFERENCES CITED The .following references are of record in the le of this patent:

NITED STATES PATENTS Number Name Date 1,152,898 McKee Sept. 7, 1915 1,614,387 Pereda Jan. 1l, 1927 1,905,185 Morris Apr. 25 ,1933 '2,244,612 Crowley June 3, 1941 2,334,583 Reeves Nov. 16, 1943 l2,378,531 Becker June 19, 1945 2,387,378 Wolk Oct. 23, 1945 2,388,055 Hemminger Oct. 30, -1945 2,393,636 Johnson Jan. 29, 1946 2,396,709 Leffer Mar. 19, 1946 2,397,485 Hemminger Apr. 2, 1946 2,399,050 Martin Apr. 23, 1946 2,441,170 Rose et al May 11, 1948 2,443,210 Upharn June 15, 1948 '2,462,891 Noll Mar. 1, 1949 FOREIGN PATENTS Number Country Date 60,147 Norway Nov. "21, 1938 

1. IN A CONTINUOUS CYCLIC HYDROCARBON CONVERSION PROCESS WHEREIN A FINELY DIVIDED ADSORBENT CONTACT MATERIAL IS PASSED CYCLICALLY THROUGH A HYDROCARBON CONVERSION ZONE WHEREIN IT CONTACTS A VAPORIZED HYDROCARBON CHARGE TO EFFECT THE CONVERSION THEREOF TO LOWER BOILING GASOLINE CONTAINING PRODUCTS AND THROUGH A CONTACT MATERIAL REGENERATING ZONE WHEREIN CARBONACEOUS CONTAMINANTS DEPOSITED UPON THE CONTACT MATERIAL DURING SAID HYDROCARBON CONVERSION ARE BURNED, THE METHOD FOR CONDITIONING A HIGH BOILING LIQUID FRACTION TO PROVIDE THEREFROM A SUITABLE VAPORIZED HYDROCARBON CHARGE FOR SAID CONVERSION ZONE WHICH COMPRISES: MAINTAINING A SUBSTANTIALLY COMPACT COLUMN OF DOWNWARDLY MOVING HEAT ABSORPTIVE MATERIAL IN A CONFINED PARTIAL CONVERSION ZONE, PASSING SAID HIGH BOILING LIQUID FRACTION INTO CONTACT WITH SAID COLUMN TO EFFECT ITS CONVERSION TO A LOWER BOILING VAPORIZED HYDROCARBON FRACTION SUITABLE FOR CHARGING TO SAID CONVERSION ZONE, SAID CONVERSION RESULTING IN THE DEPOSITION OF A CARBONACEOUS DEPOSIT UPON SAID HEAT ABSORPTIVE MATERIAL, PASSING SAID VAPORIZED FRACTION TO SAID CONVERSION ZONE AS THE HYDROCARBON CHARGE THERETO, SUBSTANTIALLY CONTINUOUSLY WITHDRAWING USED HEAT ABSORPTIVE MATERIAL BEARING CARBONACEOUS DEPOSIT FROM THE LOWER SECTION OF SAID PARTIAL CONVERSION ZONE AND SUPPLYING HEATED HEAT ABSORPTIVE MATERIAL INTO THE UPPER SECTION OF SAID PARTIAL CONVERSION ZONE AT A RATE CONTROLLED TO SUPPLY THE HEAT REQUIRED FOR THE CONVERSION OF SAID LIQUID FRACTION TO SAID VAPORIZED FRACTION, PHYSICALLY EFFECTING THE REMOVAL OF CARBONACEOUS DEPOSITS FROM SAID USED HEAT ABSORPTIVE MATERIAL, SEPARATING THE CONTACT MATERIAL FROM THE REMOVAL CARBONACEOUS MATERIAL AND PASSING IT THROUGH A SEPARATE HEATING ZONE, PASSING A SUITABLE HEATING GAS INTO CONTACT WITH SAID HEAT ABSORBING MATERIAL IN SAID HEATING ZONE TO CAUSE SAID MATERIAL TO ABSORB A SUBSTANTIAL AMOUNT OF HEAT, RETURNING THE HEATED HEAT ABSORPTIVE MATERIAL TO SAID PARTIAL CONVERSION ZONE AS THE SUPPLY THERETO, SAID HEAT ABSORPTIVE MATERIAL BEING CAPSULES CONTAINING A FUSIBLE SUBSTANCE CAPABLE OF RELEASING LATENT HEAT AT A TEMPERATURE LEVEL BELOW THAT AT WHICH EXCESSIVE CONVERSION OF SAID LIQUID HYDROCARBON FRACTION TO GAS AND COKE WOULD OCCUR AND ABOVE THAT AT WHICH SAID VAPORIZED HYDROCARBON FRACTION FORMED IN SAID PARTIAL CONVERSION ZONE WILL CONDENSE. 